US4429131A - Process for the production of 3,5-dialkylpyridines - Google Patents

Process for the production of 3,5-dialkylpyridines Download PDF

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Publication number
US4429131A
US4429131A US06/396,102 US39610282A US4429131A US 4429131 A US4429131 A US 4429131A US 39610282 A US39610282 A US 39610282A US 4429131 A US4429131 A US 4429131A
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formaldehyde
aldehyde
reaction
ammonia
solution
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US06/396,102
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English (en)
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James I. Grayson
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Lonza AG
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Lonza AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/08—Preparation by ring-closure

Definitions

  • This invention relates to a process for the production of 3,5-dialkylpyridines.
  • 3,5-dialkylpyridines are important intermediate products in the chemical industry, for example, in the production of plant preservatives or dinicotinic acid.
  • Various processes for the production of 3,5-dialkylpyridines are known.
  • 3,5-dialkylpyridines have been produced in a gas phase reaction from formaldehyde, ammonia and an aliphatic aldehyde of the formula R--CH 2 --CHO (see French Patent No. 1,332,908).
  • formaldehyde, n-butyraldehyde and ammonia 3,5-diethylpyridine was obtained at 400° C. on an aluminum silicate catalyst impregnated with lead fluoride. The yield corresponded to a conversion of 50 percent.
  • 3,5-dimethylpyridine was obtained from formaldehyde, propionaldehyde and ammonia solution. Such a process has not attained any technical importance.
  • An object of this invention is to provide a process for the production of 3,5-dialkylpyridine in short reaction times with high yields. Another object of this invention is to provide certain compositions. Other objects and advantages of this invention are set out herein or are obvious herefrom to one ordinarily skilled in the art.
  • This invention includes a process for the production of 3,5-dialkylpyridines.
  • the process includes reacting, in mixture form, an aldehyde having the formula R--CH 2 --CHO, wherein R is a straight-chained or branched alkyl radical having 1 to 6 carbon atoms, and/or an acetal of such aldehyde with formaldehyde and/or hexamethylene tetramine and/or a formaldehyde acetal and/or a polymer of formaldehyde in liquid or aqueous phase at a temperature of 180° to 280° C. in a closed vessel in the presence of ammonia and/or ammonium ions and in the presence of anions of an inorganic and/or an organic acid, both of which at 20° C. have an acid dissociation constant of 10 6 to 10 -12 .
  • a molar ratio of aldehyde having the formula R--CH 2 --CHO to formaldehyde and/or hexamethylene tetramine and/or a formaldehyde acetal is preferably from 1 to 0.5 to 1 to 1.5.
  • the anions of the inorganic and/or organic acids are inserted into the reaction solution by addition of the corresponding water-soluble alkali and/or ammonium salts.
  • the ammonium salts preferably are used in an aqueous solution in a concentration of 0.3 to 10 mole/l.
  • the process is operated at a temperature of 205° to 240° C.
  • the aldehydes having the formula R--CH 2 --CHO can be used in the form of their acetals.
  • This invention also includes a composition composed of (a) an aldehyde having the formula R--CH 2 --CHO, wherein R is a straight-chained or branched alkyl radical having 1 to 6 carbon atoms, and/or an acetal of such aldehyde (b) formaldehyde and/or hexamethylene tetramine and/or a formaldehyde acetal, and/or a polymer of formaldehyde (c) ammonia and/or ammonium ions and (d) anions of an inorganic acid and/or an organic acid, both of which at 20° C. have an acid dissociation constant of 10 6 to 10 -12 .
  • R is a straight-chained or branched alkyl radical having 1 to 6 carbon atoms
  • aldehydes having the formula R--CH 2 --CHO includes the acetals thereof, for example, propionaldehyde diethyl acetal.
  • formaldehyde includes its acetals, for example, formaldehyde dimethyl acetal, and its polymers, for example, trioxane.
  • the reaction solution In order to insert the anions (which are important for the reaction) of the inorganic and/or organic acids (which at 20° C. have an acid dissociation constant of 10 6 to 10 -12 ) into the reaction solution, the corresponding water-soluble alkali and/or ammonium salt of the acids are added to the reaction solution.
  • the salts of the acids useful in this invention are, for example, the sodium, potassium or ammonium salts of pentaboric acid, such as, ammonium pentaborate, of carbonic acid, such as, ammonium carbonate, of phosphoric acid, such as, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, dipotassium hydrogen phosphate or diammonium hydrogen phosphate, of sulfuric acid, such as, sodium hydrogen sulfate or ammonium sulfate, of hydrofluoric acid, such as, sodium fluoride, ammonium fluoride or ammonium hydrogen difluoride, of hydrochloric acid, such as, ammonium chloride, of hydrogen bromide, such as, ammonium bromide, of heptamolybdic acid, such as, ammonium heptamolybdate, of formic acid, such as, ammonium formate, of acetic acid, such as, sodium acetate or ammonium acetate, of propi
  • ammonia and/or ammonium ions For the formation of 3,5-dialkylpyridine from an aldehyde having the formula R--CH 2 --CHO in a mixture with formaldehyde, the presence of ammonia and/or ammonium ions is necessary. Whenever ammonia is used, which can be used either in a gaseous form or as an aqueous solution, it is sufficient if alkali salts of the cited acids are used. However, mixtures of alkali salts and ammonium salts can also be used. If one does without the ammonia (i.e., as a gas or as an aqueous ammonia solution), then an ammonium salt or salts, or a mixture of ammonium salt(s) and alkali salt(s) are used. PG,6
  • liquid starting materials which are not intermiscible, are used together with aqueous formaldehyde, then it is advantageous to use small quantities of homogenizing agents, such as, alcohols or cyclic ethers, for the homogenization.
  • homogenizing agents such as, alcohols or cyclic ethers
  • examples of such alcohols are alkanols having 1 to 5 carbon atoms, such as, ethanol.
  • cyclic ethers are tetrahydrofurane.
  • the process of this invention is carried out effectively with a molar ratio of aldehyde to formaldehyde and/or hexamethylenetetramine and/or formaldehydeacetal of 1 to 0.5 to 1 to 1.5, preferably of 1 to 0.8 to 1 to 1.2.
  • the reaction temperature advantageously is 180° to 280° C., effectively is 205° to 240° C. and preferably is 225° to 235° C.
  • the reaction is carried out in the liquid phase (aqueous phase) under a pressure which occurs in the case of the reaction in the closed vessel at the predetermined temperature. It is advantageous to stir the reaction batch during the reaction.
  • the quantity of the anions of the inorganic and/or organic acids used is effectively 0.1 to 3 moles, preferably 0.2 to 1.0 mole, per mole of aldehyde.
  • the starting pH value of the aqueous reaction solution is effectively between 5.0 and 12.5.
  • the addition of the aldehyde is accomplished effectively according to the measure of its consumption.
  • it is advantageous, for example, in the case of working in a 2-liter container and with the use of 350 ml of aldehyde to add the latter continuously during a 30 to 90 minute period. In the case of other conditions, corresponding addition times are to be selected.
  • the temperature is lowered to approximately ambient temperature and 3,5-dialkylpyridine is obtained from the reaction mixture in a known manner.
  • One recovery method is based on first bringing the pH value of the water phase into the basic range and then extracting the organic material from the aqueous reaction mixture with an organic solvent, such as, benzene, toluene, xylene, methylene chloride, chloroform, ether, etc. The organic solvent is then evaporated and 3,5-dialkylpyridine is obtained by fractional distillation.
  • any other desirable or useful methods for separating and obtaining the product can also be used.
  • the aqueous salt phase is composed of the originally present quantity of water in the salt solution, the unreacted quantity of ammonia and/or ammonium salt, the optionally present metal salt, the liberated acid of the ammonium salt participating in the reaction, and one mole of water for every mole of aldehyde consumed during the reaction.
  • the aqueous salt phase therefore, is concentrated with the help of any known useful process, for example, by evaporation, in order to remove the water which formed as a consequence of the condensation reaction.
  • a reenrichment of ammonia and/or ammonium salt can be achieved by introducing gaseous ammonia at ambient temperature into the aqueous solution with reformation of the ammonium salt from the optionally present acid.
  • reaction participants are introduced continuously into a suitable pressure reactor from which the reaction mixture is continuously drawn off.
  • the reaction products are separated from the reaction mixture, the aqueous salt phase is reconcentrated and unchanged reaction participants are supplemented again and returned to the reaction vessel.
  • the continuous process can be carried out in any reaction which permits an intimate intermixing of the reaction participants while stirring vigorously, for example, in a continuously-stirred tank reactor.
  • this invention involves a process for the production of 3,5-dialkylpyridine from a mixture of an aldehyde having the formula R--CH 2 --CHO and formaldehyde in the liquid phase.
  • the yield of 3,5-lutidine was 28.8 percent, based on the amount of propionaldehyde used.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
US06/396,102 1981-07-09 1982-07-07 Process for the production of 3,5-dialkylpyridines Expired - Fee Related US4429131A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH4504/81 1981-07-09
CH4504/81A CH656879A5 (de) 1981-07-09 1981-07-09 Verfahren zur herstellung von 3,5-dialkylpyridinen.

Publications (1)

Publication Number Publication Date
US4429131A true US4429131A (en) 1984-01-31

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ID=4277344

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US06/396,102 Expired - Fee Related US4429131A (en) 1981-07-09 1982-07-07 Process for the production of 3,5-dialkylpyridines

Country Status (7)

Country Link
US (1) US4429131A (de)
EP (1) EP0070012B1 (de)
AT (1) ATE30321T1 (de)
CH (1) CH656879A5 (de)
DE (1) DE3277503D1 (de)
DK (1) DK307682A (de)
IE (1) IE53300B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998014428A1 (en) * 1996-10-03 1998-04-09 E.I. Du Pont De Nemours And Company Preparation of 3,5-lutidine

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1208569A (en) * 1967-01-04 1970-10-14 Ici Ltd Process for the production of pyridines
DE2045885A1 (en) * 1970-09-17 1972-03-23 Farbenfabriken Bayer Ag, 5090 Leverkusen 3,5-dialkylpyridine prdon - from formaldehyde pre condesnates higher aldehydes
DE2045884A1 (de) * 1970-09-17 1972-03-23 Farbenfabriken Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von 3.5-Dialkylpyridinen aus alpha-alkylsubst. Acroleinen
ATE5719T1 (de) * 1980-05-23 1984-01-15 Lonza Ag Verfahren zur herstellung von 3-picolin.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998014428A1 (en) * 1996-10-03 1998-04-09 E.I. Du Pont De Nemours And Company Preparation of 3,5-lutidine

Also Published As

Publication number Publication date
EP0070012B1 (de) 1987-10-21
IE53300B1 (en) 1988-10-12
EP0070012A3 (en) 1984-03-28
ATE30321T1 (de) 1987-11-15
DK307682A (da) 1983-01-10
DE3277503D1 (en) 1987-11-26
CH656879A5 (de) 1986-07-31
IE821482L (en) 1983-01-09
EP0070012A2 (de) 1983-01-19

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